CN115779887B - Vanadium-based denitration catalyst based on rapid SCR (selective catalytic reduction) reaction, and preparation and application thereof - Google Patents
Vanadium-based denitration catalyst based on rapid SCR (selective catalytic reduction) reaction, and preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 63
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 41
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010531 catalytic reduction reaction Methods 0.000 title abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003546 flue gas Substances 0.000 claims abstract description 33
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000000428 dust Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 235000006408 oxalic acid Nutrition 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
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- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000012695 Ce precursor Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
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- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
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- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- AQGDXJQRVOCUQX-UHFFFAOYSA-N N.[S] Chemical compound N.[S] AQGDXJQRVOCUQX-UHFFFAOYSA-N 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
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- 239000002918 waste heat Substances 0.000 description 1
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Abstract
The invention relates to the technical field of catalysts, and provides a vanadium-based denitration catalyst based on a rapid SCR (selective catalytic reduction) reaction, and preparation and application thereof, wherein the vanadium-based denitration catalyst comprises a catalyst carrier and active components, and the active components comprise a main active component, a secondary active component A, a secondary active component B and a reactive auxiliary agent C; the main active component is V 2O5; the secondary active component A is WO 3 and/or MoO 3; the secondary active component B is CeO 2 and/or MnO 2; the active auxiliary agent C is C 3N4. Compared with the prior art, the vanadium-based denitration catalyst based on the rapid SCR reaction is more suitable for ultralow-temperature flue gas denitration after bag dust collection, greatly improves the ultralow-temperature section flue gas denitration efficiency, has the advantages of wide temperature activity temperature window of 100-400 ℃, no influence on kiln working condition operation, low cost and the like, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of catalysts, relates to a vanadium-based denitration catalyst and preparation and application thereof, and in particular relates to a vanadium-based denitration catalyst based on a rapid SCR (selective catalytic reduction) reaction and preparation and application thereof.
Background
At present, emission standards of various places are becoming strict, and ultra-low emission requirements are an inevitable trend of ecological environment development, wherein a selective catalytic reduction denitration technology (NH 3 -SCR) taking ammonia as a reducing agent is the most mature and efficient NO x removal technology at present. In recent years, with the basic completion of ultra-low emission modification in the power industry and the further improvement of the emission reduction requirement of NO x in China, the emission reduction emphasis of nitrogen oxides in industrial fixed sources in China is gradually changed from the power industry to the non-power industry. Because the temperature of the boiler flue gas in the non-electric industry is generally lower, especially the temperature of the kiln tail flue gas in the cement industry is in the range of 100-130 ℃, and the high-temperature SCR denitration system in the electric industry has the problem of poor adaptability on the boiler in the non-electric industry. Therefore, the application of the low-temperature SCR system in the industrial kiln is a technical problem to be solved urgently.
The cement flue gas SCR denitration process is mainly three types of arrangement forms, namely high-temperature high-dust/medium-dust, medium-temperature medium-dust and low-temperature low-dust, wherein the catalyst is a key in the technology, and the denitration temperature ranges of the catalyst which are suitable for different working conditions of an industrial furnace at present are respectively high-temperature 280-400 ℃, medium-temperature 180-220 ℃ and low-temperature working conditions lower than 180 ℃. The high-temperature high-dust SCR technology is most mature and widely applied, the denitration efficiency of the catalyst is high in a reaction temperature range, the adaptability to the high-sulfur flue gas environment is strong, the catalyst is easy to block and abrade, and the temperature drop and the system resistance can have a certain influence on the waste heat power generation; the medium-temperature medium-dust SCR process relieves the blocking and abrasion of the catalyst to a certain extent, but also has the risk of ammonium bisulfate binding blocking, and is suitable for the environment with lower SO 2 concentration; the low-temperature low-dust SCR process has the advantages of low energy consumption, small influence of kiln working conditions, low cost and the like, dust and sulfur content of flue gas after dust collection and desulfurization by a cloth bag is reduced to milligram level, physical abrasion to a catalyst and generation of sulfur ammonia salt are reduced, but the catalyst has technical bottlenecks of low-temperature denitration efficiency, easy poisoning and deactivation and the like, so that the current low-temperature SCR technology is slow in application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a vanadium-based denitration catalyst based on a rapid SCR reaction, and preparation and application thereof, which are used for solving the problems of high activation temperature, low denitration efficiency and easy poisoning and deactivation of the denitration catalyst in the prior art, wherein the catalyst is used for catalyzing and denitrating flue gas at 100-150 ℃, and the denitration efficiency is as high as more than 85%. The catalyst is modified by utilizing W/Mo acid site regulation, C 3N4 alkaline site regulation and Mn/Ce oxidation in-situ comprehensive regulation, and the catalyst is utilized in a rapid SCR reaction to realize the efficient ultralow-temperature denitration effect.
The invention provides a vanadium-based denitration catalyst based on a rapid SCR (selective catalytic reduction) reaction, which comprises a catalyst carrier and active components, wherein the active components comprise a main active component, a secondary active component A, a secondary active component B and a coagent C;
The main active component is V 2O5;
The secondary active component A is WO 3 and/or MoO 3;
The secondary active component B is CeO 2 and/or MnO 2;
the active auxiliary agent C is C 3N4.
According to the research of the invention, the specific secondary active component A and the secondary active component B are adopted to replace a part of the main active component V 2O5, and the sulfur resistance of the catalyst is improved by coupling the acid center and the redox active site on the surface of the catalyst; meanwhile, the active auxiliary agent C can promote the regulation and control of the alkaline position on the surface of the catalyst, is favorable for the adsorption of reaction gas, and comprehensively regulates the catalyst to enable the components to exert a synergistic effect, so that the obtained catalyst can exert stronger denitration and conversion capability while reducing the cost and the toxicity, and the activity temperature window of the catalyst is wider than that of the conventional V 2O5 catalyst, can reach 100-400 ℃, and has a wider application prospect, particularly in the range of 100-150 ℃.
According to the vanadium-based denitration catalyst based on the rapid SCR reaction, the mass percentage of the main active component in the catalyst is 3-10%.
According to the vanadium-based denitration catalyst based on the rapid SCR reaction, the total mass percentage of the secondary active component A and the secondary active component B in the catalyst is 1-10%.
According to the vanadium-based denitration catalyst based on the rapid SCR reaction, the mass ratio of the secondary active component A to the secondary active component B is 1:9-9:1, preferably 3:7-7:3.
According to the vanadium-based denitration catalyst based on the rapid SCR reaction, the catalyst carrier is TiO 2, preferably anatase type TiO 2. The addition of co-agent C helps to increase the binding capacity of the carrier to the active ingredient.
According to the vanadium-based denitration catalyst based on the rapid SCR reaction, the total mass percentage of the secondary active component A and the secondary active component B in the catalyst is 1-20%; the mass percentage of the secondary active component A in the catalyst is 0.5-10%; the mass percentage of the secondary active component B in the catalyst is 0.5-10%; the mass percentage of the active auxiliary agent C in the catalyst is 1-10%.
More preferably, the mass percentage of the secondary active component A in the catalyst is 5%;
The mass percentage of the secondary active component B in the catalyst is 5%;
The mass percentage of the active auxiliary agent C in the catalyst is 3%;
The mass percentage of the main active component in the catalyst is 5%.
The invention researches find that the denitration efficiency of the catalyst obtained under the condition is higher at the low temperature of 120 ℃, and the NO x conversion rate is 95%.
The invention provides a preparation method of a vanadium-based denitration catalyst based on a rapid SCR reaction, which comprises the following steps: the catalyst carrier is loaded with the active auxiliary agent C, the secondary active component B, the secondary active component A and the main active component in sequence, which is beneficial to the combination between the carrier and active metal, ensures that the active component provides optimal active sites on the outermost surface of the catalyst, simultaneously ensures that the coupled secondary active components exert synergistic effect, and improves the denitration activity and the poisoning resistance of the catalyst.
According to the preparation method of the vanadium-based denitration catalyst based on the rapid SCR reaction, which is provided by the invention, the preparation method comprises the following steps:
(1) Mechanically mixing a C 3N4 precursor and a catalyst carrier to form a CN-carrier;
(2) Adding the CN-carrier obtained in the step (1) into a precursor solution of an active component B for impregnation, removing water, drying, and roasting to obtain the active component B/CN-carrier;
The precursor solution of the active component B is prepared by the following steps: weighing a certain amount of manganese precursor or cerium precursor, and dissolving in deionized water. The cerium precursor is cerium nitrate; the manganese precursor is manganese nitrate or manganese acetate.
(3) Adding the active component B/CN-carrier obtained in the step (2) into the precursor solution of the active component A, performing rotary evaporation to remove water, drying, and roasting to obtain the active component A-active component B/CN-carrier;
the precursor solution of the active component A is prepared by the following steps: a certain amount of tungsten precursor or molybdenum precursor is weighed and dissolved in deionized water. The tungsten precursor is ammonium metatungstate; the molybdenum precursor is ammonium meta-molybdate.
(4) And (3) adding the active component A-active component B/CN-carrier obtained in the step (3) into a precursor solution of the main active component, performing rotary evaporation to remove water, drying, and roasting to obtain the catalyst.
The precursor solution of the main active component is prepared by the following steps: the vanadium precursor was dissolved in an oxalic acid solution. The vanadium precursor is ammonium metavanadate.
According to the preparation method of the vanadium-based denitration catalyst based on the rapid SCR reaction, the C 3N4 precursor is melamine.
Preferably, the temperature at which the precursor is dissolved in the second and third steps is each independently room temperature, such as 15-35 ℃;
The temperature of the precursor dissolution in the fourth step is 50 to 70 ℃, such as 50 ℃,60 ℃, 65 ℃, or 70 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the temperature of the drying in each step is, independently, 105 to 125 ℃, such as 105 ℃, 108 ℃, 110 ℃, 115 ℃, 118 ℃, 120 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the temperature of the calcination in each step is, independently, 450 to 650 ℃, such as 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃, 600 ℃, 630 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the time of calcination in each step is independently 4 to 6 hours, such as 4 hours, 4.5 hours, 4.8 hours, 5 hours, 5.5 hours, or 5.8 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The vanadium-based denitration catalyst based on the rapid SCR reaction is applied to the ultralow-temperature flue gas removal NO x of an industrial kiln; the ultra-low temperature refers to the condition that the temperature of a catalyst application window is lower than 150 ℃.
Preferably, the vanadium-based denitration catalyst based on the rapid SCR reaction is applied to ultralow-temperature flue gas denitration after cloth bag dust collection of an industrial furnace. In a preferred embodiment of the invention, the conversion of NO x is as high as 95%.
According to the vanadium-based denitration catalyst based on the rapid SCR reaction, in the rapid SCR reaction, the NO and the NO 2 in equal proportion simultaneously participate in the SCR reaction, so that the denitration reaction activity of the catalyst at low temperature can be greatly promoted. On the basis, the catalyst is modified through W/Mo acid position regulation and control, C 3N4 alkaline position regulation and comprehensive regulation and control of Mn/Ce oxidation and reduction in situ, so that the high-efficiency ultralow-temperature denitration effect of the catalyst is realized, the application range of the denitration technology is widened, and the increasingly serious environment-friendly discharge pressure and indexes are met.
Compared with the prior art, the invention has the following beneficial effects:
1. the vanadium-based catalyst provided by the invention is used for comprehensively modifying the coupling acid position, the alkaline position and the oxidation-reduction position on the surface of the catalyst, so that the denitration capacity and the sulfur poisoning resistance of the catalyst are improved.
2. The invention is based on a rapid SCR reaction, wherein NO 2 participates in the synergistic interaction with a secondary active component A, a secondary active component B and a active auxiliary agent C in the catalyst, so that the oxidation-reduction cycle of vanadium on the surface of the catalyst is accelerated, the low-temperature denitration efficiency of the vanadium-based catalyst is improved, the reaction decomposition rate of ammonium bisulfate deposited on the surface of the catalyst is accelerated, and the denitration reaction activity of the catalyst at low temperature can be promoted.
3. The invention uses the modified denitration catalyst to couple with the rapid SCR reaction, can perform denitration on ultralow-temperature flue gas after cloth bag dust collection of an industrial furnace, and has denitration efficiency as high as more than 85%.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the denitration catalytic performance of the catalysts prepared in examples 1 to 2 and comparative examples 1 to 4 under the condition that flue gas is sulfur-free and water-free;
FIG. 2 shows denitration catalytic performances of the catalysts prepared in examples 1 to 2 and comparative examples 1 to 4 under the condition that flue gas contains sulfur and water.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
The vanadium-based denitration catalyst based on the rapid SCR reaction, and preparation and application thereof according to the present invention are described below with reference to fig. 1 to 2.
For simplicity of expression, the catalyst in the examples below is named in abbreviated form, the composition of the catalyst being denoted as xV-aAbB/CN-Ti, where x denotes the percentage of the primary active component V 2O5, A denotes the percentage of the secondary active component A, a denotes the percentage of the secondary active component A, B denotes the percentage of the secondary active component B, and B denotes the percentage of the secondary active component B. The total mass of the catalyst in the examples below was 10g.
Example 1
The embodiment provides a vanadium-based denitration catalyst based on a rapid SCR reaction, and the composition of the catalyst is abbreviated as 5V-5W5Ce/CN-Ti.
The embodiment also provides a preparation method of the catalyst, which comprises the following steps:
step one: taking 0.4109g of melamine and 8.5g of TiO 2 carrier, fully and uniformly mixing, and marking as CN-TiO 2;
Step two: taking 1.2611g of cerium nitrate to dissolve in 20mL of deionized water, adding the 8.5g of CN-TiO 2 mixture, magnetically stirring and impregnating for 4 hours, drying at 110 ℃, and roasting at 500 ℃ for 4 hours to obtain CeO 2/CN-TiO2;
Step three: dissolving 0.5313g of ammonium metatungstate in 20mL of deionized water, adding the product obtained in the step two, magnetically stirring and impregnating for 4 hours, drying at 110 ℃, and roasting at 500 ℃ for 4 hours to obtain WO 3-CeO2/CN-TiO2;
Step four: heating an ultrasonic instrument to 65 ℃, dissolving 0.9895g of oxalic acid in 20mL of deionized water to prepare oxalic acid solution, dissolving 0.6427g of ammonium metavanadate in the oxalic acid solution, adding the product obtained in the step three, magnetically stirring and impregnating for 4 hours, drying at 110 ℃, and roasting for 4 hours at 500 ℃ to obtain the 5V-5W5Ce/CN-Ti catalyst.
Example 2
The embodiment provides a vanadium-based denitration catalyst based on a rapid SCR reaction, and the composition of the catalyst is abbreviated as 5V-5Mo5Mn/CN-Ti.
Step one: taking 0.4109g of melamine and 8.5g of TiO 2 carrier, fully and uniformly mixing, and marking as CN-TiO 2;
Step two: dissolving 0.9949g of manganese acetate in 20mL of deionized water, adding 8.5gCN-TiO 2 mixture, magnetically stirring and impregnating for 4 hours, drying at 105 ℃, and roasting at 500 ℃ for 4 hours to obtain MnO 2/CN-TiO2;
step three: dissolving 0.6809g of ammonium molybdate in 20mL of deionized water, adding the product obtained in the step two, magnetically stirring and impregnating for 4 hours, drying at 110 ℃, and roasting at 500 ℃ for 4 hours to obtain MoO 3-MnO2/CN-TiO2;
Step four: heating an ultrasonic instrument to 65 ℃, dissolving 0.9895g of oxalic acid in 20mL of deionized water to prepare oxalic acid solution, dissolving 0.6427g of ammonium metavanadate in the oxalic acid solution, adding the product obtained in the step three, magnetically stirring and impregnating for 4 hours, drying at 110 ℃, and roasting at 500 ℃ for 4 hours to obtain the 5V-5Mo5Mn/CN-Ti catalyst.
Comparative example 1
A catalyst which differs from example 1 only in that: the catalyst does not contain active auxiliary agent and secondary active components WO 3 and CeO 2, namely the composition is abbreviated as 5V/Ti.
Comparative example 2
A catalyst which differs from example 1 only in that: the catalyst does not contain secondary active components WO 3 and CeO 2 and only contains corresponding active auxiliary agents, namely the composition is abbreviated as 5V/CN-Ti.
Comparative example 3
A catalyst which differs from example 1 only in that: the catalyst uses equivalent WO 3 to replace the secondary active component CeO 2 and does not contain active auxiliary agent, namely the composition is abbreviated as 5V-10W/Ti.
Comparative example 4
A catalyst which differs from example 1 only in that: the catalyst does not contain active auxiliary agent, namely, the composition is abbreviated as 5V-5W5Ce/Ti.
The invention adopts a miniature performance evaluation device to test the denitration catalytic efficiency of the catalysts provided in examples 1-2 and comparative examples 1-4, and the parameters of the test method are divided into the following steps:
Test parameter 1: under standard SCR reaction conditions, the volume space velocity of the flue gas is 60000h -1,O2, the volume concentration of the ammonia gas is 400ppm, the concentration of the NO is 400ppm, and the reaction temperature is 100-200 ℃.
Test parameter 2: under the rapid SCR reaction condition, the volume space velocity of the flue gas is 60000h -1,O2, the volume concentration of the ammonia gas is 3%, the concentration of the NO is 400ppm, the concentration of the NO is 200ppm, the concentration of the NO 2 is 200ppm, the ammonia nitrogen ratio is 1:1, and the reaction temperature is 100-200 ℃.
Test parameter 3: the standard SCR reaction conditions when the flue gas contains SO 2 and H 2 O differ from test parameter 1 only in that the flue gas contains SO 2 and H 2 O, and the SO 2 concentration is 30ppm and the H 2 O volume concentration is 5%.
Test parameters 4: the rapid SCR reaction conditions when the flue gas contained SO 2 and H 2 O differed from test parameter 2 only in that the flue gas contained SO 2 and H 2 O, and the SO 2 concentration was 30ppm and the H 2 O volume concentration was 5%.
The catalysts of comparative examples 1-4, examples 1-2 were tested with and without flue gas containing SO 2 and H 2 O, and the catalyst of comparative example 1 was subjected to both standard SCR reactions and rapid SCR reactions; comparative example 2a standard SCR reaction was performed, comparative examples 3 to 4 and examples 1 to 2a rapid SCR reaction was performed, and the test results are shown in fig. 1 and 2.
As can be seen from the results of fig. 1, the denitration efficiency of the catalyst at different temperatures of the rapid SCR reaction involving 5V/Ti of the catalyst is taken as a reference line, the rapid SCR reaction can significantly improve the denitration efficiency of the catalyst, and the denitration efficiency is improved by about 60% at the reaction temperature of 140 ℃; the other catalysts have very remarkable lifting effect in the temperature range of 100-120 ℃ under the rapid SCR reaction condition, and the conversion rate of NO x at 120 ℃ is up to 98%; when the catalyst contains two or three secondary active components for compounding, the removal rate of NO x in the flue gas is far better than that of the catalyst only containing the main active components at the reaction temperature of 120-150 ℃; moreover, better removal is obtained when the specific secondary active component A, secondary active component B and coagent C of the present invention are compounded with V 2O5.
As can be seen from the results of fig. 2, when the flue gas contains SO 2 and H 2 O, the catalyst is easy to deactivate, SO that the denitration efficiency of the catalyst is reduced, wherein the denitration efficiency of the rapid SCR reaction is obviously better than that of the standard SCR without NO 2 participating in the reaction. Taking denitration efficiency of the catalyst 5V/Ti at different temperatures of the rapid SCR reaction as a reference line, the improvement effect of the 5V-10W/Ti catalyst at the temperature range of 120-150 ℃ is obviously better than that of NO x at the temperature range of 100-120 ℃ and the conversion rate of NO x at the temperature range of 150 ℃ is improved by about 35%; moreover, when the specific secondary active component A, the secondary active component B and the active auxiliary agents C and V 2O5 are adopted for compounding, better poisoning resistance can be exerted, and better removal effect can be obtained.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The vanadium-based denitration catalyst based on the rapid SCR reaction for removing NO x from ultralow-temperature flue gas of an industrial furnace is characterized by comprising a catalyst carrier and active components, wherein the active components comprise a main active component, a secondary active component A, a secondary active component B and a co-agent C;
The catalyst carrier is TiO 2;
The main active component is V 2O5;
The secondary active component A is WO 3 and/or MoO 3;
The secondary active component B is CeO 2 and/or MnO 2;
The active auxiliary agent C is C 3N4;
the preparation of the vanadium-based denitration catalyst comprises the following steps: and loading the active auxiliary agent C, the secondary active component B, the secondary active component A and the main active component on the catalyst carrier in sequence.
2. The vanadium-based denitration catalyst based on the rapid SCR reaction for removing NO x from ultralow-temperature flue gas of an industrial furnace according to claim 1, wherein the mass percentage of main active components in the catalyst is 3-10%.
3. The vanadium-based denitration catalyst based on the rapid SCR reaction for removing NO x from ultralow-temperature flue gas of an industrial furnace according to claim 1, wherein the total mass percentage of the secondary active component A and the secondary active component B in the catalyst is 1-10%.
4. The vanadium-based denitration catalyst based on the rapid SCR reaction for removing NO x from ultralow-temperature flue gas of an industrial furnace according to claim 1, wherein the mass ratio of the secondary active component A to the secondary active component B is 1:9-9:1.
5. The vanadium-based denitration catalyst based on the rapid SCR reaction for removing NO x from ultralow-temperature flue gas of an industrial furnace according to any one of claims 1 to 4, wherein the catalyst carrier is anatase TiO 2.
6. The vanadium-based denitration catalyst based on the rapid SCR reaction for removing NO x from ultralow-temperature flue gas of an industrial furnace according to claim 1, wherein the mass percentage of the secondary active component A in the catalyst is 0.5-10%; the mass percentage of the secondary active component B in the catalyst is 0.5-10%; the mass percentage of the active auxiliary agent C in the catalyst is 1-10%.
7. The method for preparing the vanadium-based denitration catalyst for removing NO x from ultralow-temperature flue gas of an industrial furnace based on the rapid SCR reaction according to any one of claims 1 to 6, which is characterized by comprising the following steps: and loading the active auxiliary agent C, the secondary active component B, the secondary active component A and the main active component on the catalyst carrier in sequence.
8. The method for preparing the vanadium-based denitration catalyst based on the rapid SCR reaction for removing NO x from ultralow-temperature flue gas of an industrial furnace according to claim 7, wherein the preparation method comprises the following steps:
(1) Mechanically mixing a C 3N4 precursor and a catalyst carrier to form a CN-carrier;
(2) Adding the CN-carrier obtained in the step (1) into a precursor solution of an active component B for impregnation, removing water, drying, and roasting to obtain the active component B/CN-carrier;
(3) Adding the active component B/CN-carrier obtained in the step (2) into the precursor solution of the active component A, performing rotary evaporation to remove water, drying, and roasting to obtain the active component A-active component B/CN-carrier;
(4) And (3) adding the active component A-active component B/CN-carrier obtained in the step (3) into a precursor solution of the main active component, performing rotary evaporation to remove water, drying, and roasting to obtain the catalyst.
9. The method for preparing the vanadium-based denitration catalyst based on the rapid SCR reaction for removing NO x from ultralow-temperature flue gas of an industrial furnace according to claim 8, wherein the C 3N4 precursor is melamine.
10. The application of the vanadium-based denitration catalyst based on the rapid SCR reaction for removing NO x from ultralow-temperature flue gas of an industrial furnace according to any one of claims 1 to 6, which is characterized in that the vanadium-based denitration catalyst is applied to the ultralow-temperature flue gas of the industrial furnace to remove NO x; the ultra-low temperature refers to the condition that the temperature of a catalyst application window is lower than 150 ℃.
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